Gas hydrates are clathrates (inclusion compounds) of gases in a lattice consisting of water molecules.
Low-boiling hydrocarbons, such as methane, ethane, propane, butane and iso-butane, are present in natural gas and also in crude oil. Because water may also be present in varying amounts in natural gas and crude oil, the mixture, under conditions of elevated pressure and reduced temperature, tends to form gas hydrate crystals. The maximum temperature at which gas hydrates can be formed strongly depends on the pressure of the system. For example, ethane at a pressure of approximately 1MPa can form hydrates only at temperatures below 4.degree. C. whereas at a pressure of 3 MPa stable hydrates can be present at temperatures as high as 14.degree. C. With respect to this strong dependence of the hydrate melting point on pressure, hydrates markedly differ from ice. As described by M. von Stackelberg and H. R. Muller (Z. Electrochem. 1954 5825), methane and ethane hydrates form cubic lattices having a lattice constant of 1.2 nm (hydrate structure I). The lattice constant of the cubic propane and butane gas hydrates is 1.73 nm (hydrate structure II). However, the presence of even small amounts of propane in a mixture of low-boiling hydrocarbons will result in the formation of gas hydrates having structure II (J. H. van dor Waals and J. C. Platteeuw, Adv. Chem. Phys. 2 1959 1).
It has been known for a long time, that gas hydrate crystals, when allowed to form and grow inside a conduit such as a pipeline, tend to block or even damage the conduit. To prevent such blocking, the following thermodynamic measures are possible in principle: removal of free water, maintaining elevated temperatures and/or reduced pressures or the addition of melting point depressants (antifreeze). In practice, the last-mentioned measure is most frequently applied. However, the antifreeze, such as the lower alcohols and glycols, have to be added in substantial amounts (several tens of percent by weight of the water present) to be effective. An additional disadvantage of such amounts is that recovery of the antifreezes is usually required during further processing of the mixture.
An attractive alternative to the anti-hydrate measures described above, particularly the antifreezes, is to use a crystal growth inhibitor. The principle of interfering with crystal growth is known.
Plants and poikilothermic animals such as insects and cold-water fish are known to protect themselves from freezing, both by antifreezes such as glycols and by special peptides and glycopeptides (termed Antifreeze Proteins, AFP's and Antifreeze Glycoproteins, AFGP's) which interfere with ice crystal growth (A. L. de Vries, Comp. Biochem. Physiol, 73 1982 627). The present applicants found such cold-water fish peptides and glycopeptides also to be effective in interfering with the growth of gas-hydrate crystals. However, their production and use for this purpose are currently considered to be uneconomical.
In PCT Patent Application EP93/01519, the use of polymers and copolymers of N-vinyl-2-pyrrolidone for inhibiting the formation, growth and/or agglomeration of gas hydrate crystals is disclosed.
It is therefore an object of the present invention to provide a method to inhibit formation of hydrates in streams containing at least some light hydrocarbons and water. It is a further object to provide such a method wherein a high concentration of additive is not required.